Production of lubricating oil



May 27, 1952 VISCOSITY, SAYBOLT UNIVERSAL SECONDS w. M. THAW ETAL2,597,910

PRODUCTION OF LUBRICATING OIL FROM WAX Filed Feb. 28, 1950 A.S.T.M.STANDARD VISCOSITY-TEMPERATURE CHARTS FOR uoum PETROLEUM PRODUCTS(D34I-43) CHART A: SAYBOLT UNIVERSAL VISCOSITY CHART 1VISCOSITY-TEMPERATURE RELATIONSHIP OF WAX OILS COMPARED TO A STRAIGHTLINE FUNCTION CURVE I-STRAIGHT LINE CURVE 2 OIL WT-99-3 TABLE II CURVE 3OIL WT-III-Il TABLE I! 20 00 I00 I20 I40 I60 I ZIOI TEMPERATURE,F. INVENTORS Wallage M. Thaw Ha rold R. Srewarf BY: W

A; TORNEIS Patented May 27, 1952 PRODUCTION OF LUBRICATIN G OIL FROM WAXWallace M. Thaw, San Pablo, and Harold R. Stewart, Point Reyes Station,Calif., assignors to California Research Corporation, San Francisco,Calif., a corporation of Delaware Application February 28, 1950, SerialNo. 146,909 4 Claims. (01. 196-78) This invention relates to hydrocarbonlubricating oils characterized by extremely high viscosity indices andto a process for the production of such oils from petroleum waxes.

The oils of this invention are produced by chlorinating a petroleum wax,dehydrochlorinating at least a part of the product of the chlorinationstep under conditions adapted to produce a relatively saturated oil, anddewaxing the oil to separate unreacted wax from the product oil. Theproperties of the oil are critically related to the degree ofchlorination of the chlorinated wax charged to the dehydrochlorlnationstep, and to the reaction conditions and catalyst employed in thedehydrochlorination step. The oils produced are of complex chemicalcomposition and cannot be defined in terms of the amounts of specificcompounds of which they are composed but must :ratherbe defined in termsof the proces by which -,-thy are produced.

.f Injt he past, lubricating oils have been prepared i froin'p'etroleumwaxes by processes including steps of chlorination anddehydrochlorination but the products of these processes have beencharacter iz'ed by high degree of unsaturation and by high Conradsoncarbon values. In the past it has been [,considered that the productionof these oils could be effected equally as well at a wide range ofchlorination levels and the dehydrochlorination step has been conductedat relatively low temperatures with the result that the product washighly unsaturated even when prolonged process ing periods wereemployed. The oils prepared in the past have been characterized byinstability and by a tendency to lay down heavy engine deposits duringengine operation; they have not been produced commercially.

It is the primary object of this invention to produce from petroleumwaxes a substantially saturated hydrocarbon oil characterized by a highviscosity index, by a low Conradson carbon value, and by clean operationwhen employed in internal combustion engines as a lubricant.

It is a further object of this invention to protime from petroleum waxesa substantially saturated hydrocarbon oil characterized by a low pourpoint and well adapted to use in internal combustion engines operatedintermittently under low temperature conditions.

It has now been found that hydrocarbon oils of very high viscosityindex, low bromine number, and low Conradson carbon value may, beproduced by contacting a chlorinated petroleum wax consistingpredominantly of monochlorinat ed wax molecules with a silica-aluminacatalyst at an elevated temperature in exces of 550 F., but below thetemperature at which appreciable cracking occurs and preferably in therange 575 to 725 F. for a time suflicient to remove substantially all ofthe chlorine from the chlorinated wax as hydrogen chloride and toproduce a substantially saturated oil. The chlorinated wax consistingpredominantly of monochlorinated wax molecules is suitably preparedeither by controlled chlorination ofthe wax to produce a chlorinationreaction product mixture having a chlorine content less than 16% byweight and preferably in the range 612% by weight,-or by chlorinatingthe wax without attempting to carefully control the chlorine content ofthe reaction product and then subjecting the reaction product toadsorption fractionation to separate a fraction having a high content ofmonochlorinated wax molecules.

In the production of the oils of this invention, process variables suchas the degree and temperature of chlorination, the temperature duringdehydrochlorination, the type and amount of catalyst employed in thedehydrochlorination step, and the time of contact between thechlorinated wax and the catalyst :during the dehydrochlorinatlon stepmust be maintained within critical ranges and are preferably coordinatedwithin these ranges in order to produce a product oil of high viscosityindex, of substantially saturated structure as determined by brominenumber, and exhibiting a low Conradson carbon value.

The effect of varying process conditions upon the product quality andthe boundaries and significance of the particular ranges of operatingconditions described and claimed herein are illustrated by the examplesand by the experimental data relating to the variation of particularprocess conditions set forth hereinafter.

Example .L-A sample of crude scale Wax was chlorinated to a degree suchthat the unreacted wax plus the chlorinated wax produced had a chlorinecontent of 8% by weight. The reaction product was then cooled andsweated at room temperature to separate chlorinated wax from unreactedwax. The resultant chlorinated wax had a chlorine content of 11.7% byweight and a considerable content of dissolved wax which was removedfrom the reaction product with the chlorinated wax during the sweating.

A portion of this chlorinated wax was melted, mixed with 10% by weightof Florida clay, and heated to 500 F. over a period of 2 hours whilestirring and then held at a temperature of 500 F. for 2 hours. Themixture was then cooled 1 and filtered to separate the clay from theoil. The properties of the oil are set forth in the first column ofTable I below. A second portion of the chlorinated wax described abovewas mixed with by weight of Filtrol clay (a natural clay activated byacid treating and sold under the trade name of Filtrol) heated duringagitation over a period of 2 hours to a temperature of 650 F. and heldat that temperature for minutes. The reaction product was cooled andfiltered to separate the clay. The properties of the oil are set forthin the second column of Table I following.

TABLE I Feed Stock Scale Wax Scale Wax Run Number WT-l-ZGB WT-l26iChlorination:

Per cent Chlorine in Chlorinated War. 11. 7. .7. Temperature, "F170-190.... 170-190. Final Process Step...

Per cent Catalyst. Temperature, F Time in Minutes" Inspection onProducts:

Per cent Remaining Chlorine W eight. Viscosity at 100 F., SSU Viscosityat 210 F., SSU Viscosity Index Bromine Number Molecular WeightUnsaturation, M01. per cent Pour Point, "F Per cent Wax by weight FlashPoint, F., Cleveland Color, ASTM Conradson Carbon, per cent 1Dehydrochlorination Florida Clay.

i Dchydrochlorination and Saturation Filtrol Clay.

It will be noted that the oil produced by dehydrochlorinating at 500 F.for a much longer period of time has a substantially higher brominenumber and mol per cent unsaturation based on one double bond permolecule than does the oil produced by dehydrochlorinating at 65 F. fora shorter period of time.

The viscosity indices of both oils are high, the oil produced bydehydrochlorinating at 650 F. being somewhat superior in this respect.

As might be expected from the difference in degree of saturation of thetwo oils, the oil produced by dehydrochlorinating at 650 F. was markedlysuperior in respect to oxidation stability.

The scale wax employed as the starting material had an appreciable oilcontent; an appreciable quantity of this oil made its way through theprocess steps and appeared in the product oils. The small difference inConradson carbon values of the two samples is believed to be due to thismaterial.

Example 2.Two oils designated in the following Table II as S-1 and 8-23were prepared by chlorinating petroleum wax and dehydrochlorinating thechlorinated wax under different conditions. Oil S1 was prepared bychlorinating petroleum wax to a chlorine content of 25% by weight onbasis of reaction product. The chlorinated wax was dehydrochlorinated at600 F.

Oil S-23 was prepared by chlorinating petroleum wax to a chlorinecontent of 8% by weight based on the reaction product,dehydrochlorinating at 600 F. and dewaxing. The chlorinated waxmolecules contained in the reaction product were predominantlymonochlorinated molecules.

The catalyst employed in the dehydrochlorination step in producing bothof the oils was Filtrol clay. The properties of these oils aresummarized in the following Table II:

' a period of about two hours,

1 S-1 after clay treatment.

It will be noted that oil 8-23 produced by chlorinating the petroleumwax to a much lower chlorine content is markedly superior to oil S-l inrespect to viscosity index and in respect to carbon residue.

It will be noted also that 011 8-10 produced by subjecting oil 3-1 toconventional clay treatment is somewhat superior to 8-1 but is markedlyinferior to 8-23.

Oil 8-1 was compared with a highly refined commercial hydrocarbon oil intest runs in a Wisconsin engine operating at 550 F. cylinder temperatureand 220 F. oil temperature. Oil 8-1 was noticeably inferior to thecommercial oil in respect to piston deposit number and percent of oilring clogging.

Oil 6-23 was compared with a highly refined commercial lubricating oilin test runs in a Lauson engine operated at a cylinder temperature of375 F. and an oil temperature of 300 F. At the end of 60 hours pistondeposits for both oils were low and no oil ring clogging was observedwith either oil.

Example 3-The oil described in Table III below demonstrates that oils ofhigh quality may be prepared from low value waxy refinery streams by theprocess of this invention.

A distillation cut from slack wax containing 27.3% oil and having amolecular weight of 490 was chlorinated to 9.0% by weight based onreaction mixture. The chlorinated charge wa mixed with 15% by weight ofFiltrol clay, and the mixture was heated, with agitation, to 640 F.during The temperature of the mixture was held at 640 F. for one hourafter which the dehydrochlorinated mixture was cooled and filtered freefrom clay. The stock was then dewaxed at -l0 F. The dewaxing solvent wasremoved by distillation and the oil was vacuum distilled to 415 1 pottemperature at 2 mm. pressure. The following, inspections were obtainedon the oil:

TABLE'III Viscosity at F. SSU 281.1 Viscosity at 210 F. SSU 53.4Viscosity index 114 Molecular weight 500 Bromine number 5 Flash point,F. Cleveland Pour Point F +5 Conradson carbon, per cent 0.26 Per centchlorine by weight 0.14

commercial refining, The feed to the process ofthe invention may beslack wax, or crude scale wax, or a highly refined wax. The.oilsproduced by the process or the invention appear to be the thisdegraded material in the product oil causes a significant increase inthe rate at which engine deposits accumulate during use of the oil asalubricant.

It has been found that the yields of oil produced by the process of thisinvention under identical operating conditions, are substantially higherif waxes of relatively high molecular weight are charged to the process.If a wax having a molecular weight below about 350 is charged to theprocess, the yield of oil which is obtained is appreciably lower than ifwaxes of molecular weights of 350 and above are charged to the process.

The efiect of molecular weight of the charging stock is clearly shown bythe runs summarized in Table IV below. A wax containing approximately 21carbon atoms in each molecule was used in the first run (WT-99-3). Acommercially available scale wax having about 29 carbon atoms to themolecule was used in the second run (WT-lll-ll). Both waxes werechlorinated to the same degree in the sense that the same average numberof chlorine atoms were introduced into each charge molecule, namely, 1.1chlorine atoms per molecule. Batch dehydrochlorinations were conductedunder conditions adapted to produce substantially saturated oils. Lowpour oils were obtained from the dehydrochlorination productfig dewaxingat 50 F. in each case. Light en. were vacuum distilled to raise theviscosity of the bottoms into the lubricating oil range.

The properties of the two oils and the yields obtained from the waxes oftwo different molecular weights are shown in the following Table IV:

TABLE rv Efi ec t'; of charging stock molecular weight Run VVT-99-3WT-lll-ll Feed Stock:

Molecular Weight 300 410 Melting Point, F 94 124-126 Per Cent oil byweight 2.6 4. 7 Chlorination:

Temperature, F 190 190 Weight Per Cent Chlorine in Product 11.9 8. 7Dchydrochlorination:

Filtrol Clay 16 15 Temperature, F 550-580 550-590 Time in Minutes 30 30Dewaxing Solvent Temperature, F 50 50 Inspections on Oil:

Pour Point, F 45 9 -45 Viscosity at -30 F., SSU... 11, 250 14, 378Viscosity at F., SSU. 2, 781 Viscosity at 100 F., SSU 110. 4 119. 5Viscosity at 130 F., SSUZ- 74. 2 Viscosity at 210 F., SSU 41. D 42.1Viscosity Index 123 129 Vapor Pressure at 380 F., mm. Hg 4.8 Yields(weight percent of Charge Wax):

Inspected Oil 23v 9 31. 3 Waxy Residue 42. 0 54. 7 Light Stock, Coke,Hydrogen 33. 96 13. 97

1 Methyl Isobutyl Ketone.

2 Stable pour.

It is clear from the data presented in the above Table IV that the oilyields from waxes of higher molecular weight are substantially greaterthan P content of 11.7%

from those of low molecular weight. Explora tion of the relationshipbetween molecular weight of the charge wax and ultimate yield of, oil bythe process of this invention indicates that charge waxes having atleast 25 carbon atoms per molecule or an average molecular weight aboveabout 350 should preferably be selected for treatment by the process.

The chlorination step of the process is conducted by heating the Wax toa temperature sufficient to melt it and then bubbling chlorine gasthrough the molten wax at a moderately elevated temperature Whilevigorously agitating the molten wax.

The temperature at which the chlorination is effected is ordinarily inthe range about 250 F. If higher temperatures are used, for example, atemperature of 250 F., a tendency toward decomposition of thechlorparafiins formed during the chlorination step is observed.Decomposition of the chlorinated wax has an adverse effect on oil yieldsand an increase in the number of polychlorinated wax molecules in thechlorination reaction product has an adverse effect on the quality ofthe "oil produced. It should be noted that if the wax charge issubstantially tree of dissolved oxygen or air and if the chlorination isconducted in the absence of air, temperatures up to about 300 F. may beemployed.

A chlorinated wax consisting predominantly of monochlorinated Waxmolecules suitable for charging to the dehydrochlorination step of theprocess can be prepared by limiting the amount of chlorine introducedinto the wax during the chlorination step so that the chlorinated waxproduced has a chlorine content less than 16% and preferably in therange about 6-12% by Weight based on the whole chlorination reactionproduct mixture.

A recently developed method for separating monochlorinated wax moleculesfrom polychlorinated wax molecules has been employed to separate afraction consisting predominantly of monochlorinated wax molecules fromthe chlorinated Wax. This method is eiTective whether or not thechlorination is controlled so as to produce a reaction product having amaximum chlorine content of 16%. According to this method, the reactionproduct of the chlorination from the adsorbent is complete, benzene isemployed to desorb the polychlorinated waxes from the adsorbent. Theadsorbent mayjbeycondi- .tioned for reuse by washing the benzene fromparafiinic hydrocarbon the adsorbent with a hot such as isopentane.

A sample of crude scale wax waschlorinated to a chlorine content of 8%by weight of the reaction mixture and chlorinated wax was thenseparatedfrom. the reaction mixture by sweating.

The resulting chlorinated wax had a chlorineby weight. The chlorinateddehydrochlorinated. When the removal of the monochlorinated wax meare-.1

wax: avas-then separated-mm: contactrwithrsilica; gel. :intom-waxsfraction,-. a lmonochlorinated,wax; fraction,.-. and A apolychlorinated. wax refraction-1: The' waxiifraction amounted-to 13% byweight w of .sthdc reaction 7 mixture; 7 the .;monoohlorinated: owaxiraction amounted; .to 50% by weight of they reaction:mixture,-,andthe polychlorinated :wax'. fraction amounted to,c34'% by weight; of: thereaction-.mixturen Thus, upward rofrsixty per cent of the chlorinatedwax molecules wasmonochlorinated-owaxe; Ina second experiment a refinedwhiter-parafiin wax having amolecularweight: in.

the rangeriSflSOdwas chlorinatedtoa chlorine;

held atzthis temperature ionminutes; The

reactionressel and stock were then cooled: rapids ly and the stock wasfiltered at 150 F. tolsepa. i

arate::the; catalysts Both. products were vacuum distilled-to; 390?- F..pot; temperature at. 5 mm. pressure. Samples ,of the; twodehydrochlorihatedstocks were, solvent ,dewaxed .;at. '-10F.- totseparate, :a waxy :oil and. the 1 filtrates were again;dewaxediianrm?F. to separatei'a high; pour.;oil and :a low pour oilinreach case. In:spectionston theseaoilstare shown in the follow.- ingiTableV:

8 atoms :eaclr amolecula; The; monochlorinateda'n oils :are:markedlyisuperiorto: theupolychlorinatedr oils rin respect toRamsbottomrcarbonuand, Con-5. radson carbon. valuesz; .Eurthen;v themonoohloe: rinated oilslhave 'lowerJbrominenumbers and are"; superiorin:respect to stability:

The monochlorinated; ioils :vandr, the: po1ych1o-.= rinated,oils.:described; in the: aboveyTableV were fractionated; bysilica geladsorption intoxseveratw. cuts .5 which are: subjected ;;to:spectrographic 2." analysis: by; means ofinfrared and ultraviolettechniques: These inspections:indicated:that the; wholedehydrochlorinated stock obtainedrj:fromi'= the monochlorinated v wax;';contained :180 by Weight of .isoparaffinsglLB Zbyweightpi: monoz-i;nuclearmompounds, and-x:8.7%;- OfQLIJOIYIIUCIEQ compounds; while thewhole dehydrochlorinated stock .';obtained from--the.vpolych1orinated1-. wax: contained 48% {of ,:isoparaffins,; 34 I;oi;.mor onu v clear: compounds and; 18 of. polynuclear- -;com- 1pounds; Ramsbottom, carbonrpvaluesv for.-;:the isoparafiinic cut; themononuclearcompound" out: and the polynuclear compound out were .01,.31; and 1.57, respectively; From theforegoing'itclear that; a highcontent of polychlorinatedE wax; in the chlorinated wax produced-inthe'chlorin'ation step :of theprocess of this invention is to-be;avoided.- It may be avoidedeeither'bycontrolling .1. the chlorination tokeep ,the; chlorine contentaof the chlorinated wax I below- 16% byweight; and: preferably. in the range 6-12% "-byweight ortthe reactionproduct ofthe, chlorination step ;may; be separated byselectiveadsorption:toseparate a. monochlorinatedwax" fraction which. ischarged to the dehydrochlorination step of :the 1: process. It is alsoclear that the oil produced:inzthedeer hydroohlorination step may.desirably ,-;.be: sep-paratedby adsorption employing an adsorbent of;the silica gel type 'Such as silca. gelitself orzsilica: r

TABLE V Monochlor oils "Polychlor" Oils H1018 Vh'dle Stock Den High LowHigh Low We Pour Pour Dehydm Waxv Pour P chlorinated xy 7 chlorinatedStock, on 011 Stock on on I A B C II. 1 2 3 Inspections Vi'scoslty-at30? F .,-,SSU Viscosity at 10093.. SSH; Viscosity at 210 sson Viscosityindexecu a W t-- Color, ASTM; Gravity;-API. Percent .Oilby weight VaporPressure at 380 I*,., mm. Hg. PetcentvOhlorine by weight Carbon AtomsAva) End-Carbon Atoms (Ave) 1Percent Aromaticsby weight Yie in.

Weight- Percent ":01 '"Isomerized Stock}? 1 Corrected-1110i-oilpresent:3 Bysilica gel fractionation; 3 Basis 1001b. scale wax yields theremaining oils were compared by infrared spectra.

35 pounds of monochlorinatedwaxirom which 25.7 pounds of wholedehydrochlori-- ranted-stock! isobtainedand 25.9 pounds ofpolychlorinatedwax from which 18.0 pounds of whole dchydroohlorinatedstock' II is obtained.

The umonochlorinated-waxr from" which the monochlorinated :oils in theabove table were produced, contained-1.0 chlorine atoms permolecule.-\whi1e1..the polychlorinated wax from which silica-aluminacatalystiand at an elevated .tenrfl perature in excess of 550 F. butbelow the temperature at which appreciable cracking occurs, preferablyin the range 575-725 F.

Experiments were conducted in which a whole chlorinated wax wasdehydrochlorinated in the presence of by weight of Filtrol clay attemperatures of 500, 600, 650, 700, and 740 F. At 500 F. thedehydrochlorinated product had a high bromine number which was onlyslightly reduced by holding the oil in contact with the catalyst at thattemperature for a long period of time. At the higher temperatures thebromine number was lower and fell rapidly to a value of 3 or 4 in lessthan one hours contact. At 740 F. continuous cracking at a low rate wasobserved in the reactor indicating that a maximum temperature betweenabout 700 and 740 F. should be maintained in order to avoid cracking andobtain high oil yields.

A number of catalysts was tested for effectiveness in producingrelatively saturated hydrocarbons in the dehydrochlorination step,including synthetic silica-alumina catalyst commercially produced foruse in catalytic cracking, Filtrol clay (trade name for an acid-treatedMontmorillinite group clay high in silica and alumina) Florida clay,dehydrated Filtrol clay, silica gel, alumina, activated charcoal, andCelite (a diatomaceous silicon dioxide). Experiments showed thatsilica-alumina catalysts either natural or synthetic were markedlysuperior to the other catalysts tested in respect to producing asaturated oil.

The dehydrochlorination step of the process was conducted in a series ofparallel experiments in which only the per cent of catalyst added to thechlorinated wax was varied. During these tests the weight per cent ofcatalyst added to the reaction mixture was varied from 0 to 20% by Weiht. The experiment showed that at least 57 byweight of catalyst shouldbe employed in order to produce a saturated oil in a reasonable periodof time and that the amount should preferably be in the range 8 to 13%by weight. No

disadvantage attended the employment of larger amounts of catalyst otherthan the process burden of ltering and handling large volumes of solidmterial.

W n the chlorination step of the process is con ucted in the mannerindicated above to produoe predominantly monochlorinated wax mole cules,the reaction product of the chlorination step contains substantialamounts of unreacted wax which must be removed either from the reactionproduct of the chlorination step or from the final oil in order toobtain oils of low pour point. Accordingly, a dewaxing step is includedin the process; it may be conducted immediately following thechlorination step or immediately following the dehydrochlorination step.It is preferred to dewax the final oil produced in thedehydrochlorination step since the formation of minor amounts ofmicro-crystalline wax is sometimes observed during thedehydrochlorination.

The dewaxing is accomplished by a conventional solvent dewaxing usingsuch solvents as methyl ethyl ketone-benzene, propane, or methylisobutyl ketone.

The time of contact between the catalyst and the chlorinated wax in thedehydrocalorination step necessary to produce a substantially saturatedoil varies inversely with both thetemperature and with the amount andactivity of the catalyst employed. In a batch dehydrochlorination at 700F. using 8-12% by weight of Filtrol clay,

shows a graphical comparison of oil WT-99-3 and twenty, to thirtyminutes contact is suitable. In a continuous dehydrochlorination stepshorter contact times suffice. In the practice of the process the timeis preferably treated as a dependent variable and simple tests permitits adjustment after other conditions'have been established to produce aproduct oil of 0 to 4 bromine number. Longer contact times than thosenecessaryto produce the desired degree of saturation should beavoided asexcessively long contact times increase the production of undesiredheavy and light side reaction products.

v The oilsof this invention, as exemplified by samples WT-99-3 andWT-ll1-11 described in Table IV above have properties which make themvery valuable-as lubricants for engines operated in very cold climates.The oils show viscosities above 40 SSU at 210 F. and at 30 F. their vis.cosities. are substantially below 18,000 SSU, a common specificationfor an oil designed for use at very low temperatures. Engine consumptionof these oils as determined in comparative tests was found to be lowerthan the engine consumption for a 10/ 10W refined Pennsylvania oil.Oxidationstability of these oils was determined at high temperatures ina Chevrolet engine. Oxidation of an oil produces acids which attack themetal surfaces of the engine so a measure of this property may be madeby determining the loss in the connecting rod bearing weight, a commonvalue for a finished lubricating oil is 40-50 mg. A loss in weight foroils produced by the process of this invention was 4 mg. The oils ofthis invention have a further valuable characteristic which renders themparticularly suitable for use at extremely low temperature conditions.This is illustrated by the appended drawing which WT-lll-ll, describedin Table IV above, with a theoretical oil having a viscosity of 40 SSUat 210 F., a viscosity of 18,000 SSU at -30 F. and a straight lineviscosity-temperature relationship. Curves 2 and 3 of the graphrepresenting the oils of this invention are concave when viewed from thetemperature axis and show smaller viscosity increases as temperature islowered than those shown by the theoretical oil. Both Curve 2 and Curve3 drop below Curve l as the temperature is lowered below 0 F. Thedownward turn of these curves is important since it represents largeactual differences in viscosity at -30 F. It also means that relativelyhigher viscosities above room temperature may be had while meetmg thelow temperature viscosity requirement.

A new hydrocarbon lubricating oil and a process for producing it havebeen described above and illustrated in the foregoing examples. Variousmodifications of the process may be made by those skilled in the artwithout departing from the scope of the appended claims.

We claim:

1. A process for producing lubricating oil from petroleum wax whichcomprises chlorinating petroleum wax at a temperature below 300 F. to adegree such that the reaction product has a chlorine content less than16% by weight, mixing the resultant chlorinated Wax with at least 5% byweight of a silica alumina catalyst, heating the mixture of chlorinatedwax and catalyst to a temperature in the range GOO-725 F., maintainingthe mixture of chlorinated wax and catalyst at said temperature for atime sufiicient to effect substantially complete removal of the chlorinefrom the chlorinated wax and to produce a substantially saturated oil.

2;A process for the production of lubricatin oil from; petroleum waxwhich; comprise chlorinatinga petroleum wax: at a temperature of 100-250F; to produce a reaction: product having a chlorme content in the range6-12% by weight; dehydrochlorinating' the resultant-- chlorinated waxby: mixing theclilorinated wax with at 'least 5% by-weight' of'a silicaalumina catalyst, heating thesmixture of chlorinatediwax and catalyst toa temperature in the range 600-725" F., maintaining the mixtureof'chl'orinated wax' and catalyst within said temperature-rangefor atime suflicient to substantially completely remove the chlorine from thechlorinated wax and-to produce a substantially-saturated oil, separatingthecatalyst from the'oil and dewaxing the oil to remove unreaoted wax.

3. A process forproducing'lubricating-oil from wax" which comprisesmelting the wax and heating it toa temperature in the range IOU-250 F.,I

passingchlorine gas through the hot wax in amount sufficient only toconvert a major proportionof the wax tomonochlorinatecl wax, mixing theresultant chlorinated wax with 843% by weight of a silica aluminacatalyst, heating the A mixture of chlorinated wax and catalyst to atemperature in the range GOO-725 FE, and maintaining the chlorinated waxand catalyst at a temperature in said range for a time sufficient tosubstantially. completely remove the chlorine from the chlorinated: waxand to produce a substantially saturated oil; separating: catalyst" fromtheoilianfi dewaxing the oil'jto separate unzreacted waxfrom'the'prcduciioil.

4; A process fcr'theproduction of. athighl-yisoparafiinic. lubricatingoil. from petroleum. wax which comprises. contacting a chlorinated;petroleum waxconsistinepredonfinantly otimonochlorinated: wax molecules:with. m silica-alumina catalyst at: a temperature; in the; range:600425? Fi for a timeesuifici'enttosubstantiallycompletely remove thechlorine from the. chlorinated" wax by dehydrochlorination and;contacting the reaction product of the. dehycli'ochlorination stepwith asolid adsorbentselectect from the: group consisting' of silica gel;silica aluminat gel and alumina gel to separate an, adsorbatecompri'singaromatic hydrocarbons and a. percolate: consisting: essentially ofisoparafilnichydrocarbons.

WALLACE M. HAROLD R. STEWART.

REFERENGES CITED- The' following, references are or record in the tileofthis patent UNITED/ STATES PATENTS Number Name. Date 2,094,593Gardiner et a1. 0.011.. 5, 1939 2,384,311 Kearby -v Sept. 4, 19:45 3;2,401,636 Haensel. et a1. June 4: 19.46

1. A PROCESS FOR PRODUCING LUBRICATING OIL FROM PETROLEUM WAX WHICH COMPRISES CHLORINATING PETROLEUM WAX AT A TEMPERATURE BELOW 300* F. TO A DEGREE SUCH THAT THE REACTION PRODUCT HAS A CHLORINE CONTENT LESS THAN 16% BY WEIGHT, MIXING THE RESULTANT CHLORINATED WAY WITH AT LEAST 5% BY WEIGHT OF A SILICA ALUMINA CATALYST, HEATING THE MIXTURE OF CHLORINATED WAX AND CATALYST TO A TEMPERATURE IN THE RANGE 600-725* F., MAINTAINING THE MIXTURE OF CHLORINATED WAX AND CATALYST AT SAID TEMPERATURE FOR A TIME SUFFICIENT TO EFFECT SUBSTANTIALLY COMPLETE REMOVAL OF THE CHLORINE FROM THE CLORINATED WAX AND TO PRODUCE A SUBSTANTIALLY SATURATED OIL. 